JP5872587B2 - Process for producing transition metal hydroxides - Google Patents

Description

  The present invention relates to a method for producing a transition metal hydroxide having an average particle diameter in the range of 6 to 12 μm (D50), wherein at least one solution of at least one transition metal salt is contained in a predetermined stirring vessel. Together with a solution of at least one alkali metal hydroxide, and thereby produce an aqueous suspension of the transition metal hydroxide, and within at least one further section, respectively, In part, it relates to a process characterized in that mechanical power is continuously applied to a part of the suspension in the range of 50 to 10,000 Wl and the part is then returned to the stirring vessel.

  The present invention further relates to particulate transition metal hydroxides that can be produced, for example, by the process of the present invention.

  Secondary batteries, accumulators, or “rechargeable batteries” can be used (used) to store electrical energy after manufacture and on demand (just) in some implementations It is a form. Due to the apparently improved power density, in recent years batteries have been developed that have moved away from water-based secondary batteries and charge transport is carried out by lithium ions.

  Due to the characteristics of the lithium ion battery, the electrode material has a decisive significance. Here, the lithium-containing transition metal mixed oxide has a special significance, for example, spinel and mixed oxide provided in a layered form, particularly lithium-containing mixed oxides of nickel, manganese, and cobalt. For this, reference is made to Patent Document 1 (EP 1189296). Here, not only the stoichiometry of the electrode material, but also other properties such as morphology and surface properties play a predetermined role.

In order to produce the corresponding mixed oxide, a two-step (two-stage) process is usually used. In the first step, a (slightly) insoluble salt of one or more transition metals is produced by precipitation from solution (eg, carbonate (carbonate) or hydroxide (hydroxide)). This (slightly) insoluble salt is often referred to as the precursor or “precursor” in English. In the second step, the precipitated metal salt (s) is mixed with a lithium compound, such as Li ₂ O ₃ , LiOH or LiO ₂ and calcined at a high temperature, eg 600-1100 ° C. .

  Conventional lithium ion batteries have the potential to be improved, especially with respect to energy density. For this purpose, the cathode material should have a high specific capacity. Furthermore, this is advantageous if the cathode material can be processed in a simple (easy) manner into an electrode layer with a thickness of 20 μm to 200 μm (this electrode layer is possible per unit volume) In order to obtain as high an energy density as possible, it should have a high density).

Patent Document 2 (WO2009 / 024424) discloses a method for producing a basic transition metal hydroxide, which is composed of three steps. These processes are characterized as follows:
a) facilitating at least a first and second starting solution (free body solution);
b) introducing at least the first and second starting solutions into the reactor and forming a homogeneously mixed reaction zone and supersaturated by setting an excess of alkali with the insoluble product; forming a product suspension with a mother liquor having a pH value of 10-12, wherein the reaction zone has a specific mechanical output input of at least 2 watts / liter,
c) Partially removing the mother liquor from the precipitated product and setting a solids content of at least 150 g / l in the suspension by purification or filtration elements.

EP1189296 WO2009 / 024424

  Introducing larger mechanical energy values at large volumes of solutions or suspensions is instrumental.

  Accordingly, an object of the present invention is to provide a battery (battery) having a volume energy density as high as possible. In particular, it is an object of the present invention to provide a starting material for a battery that is suitable for the manufacture of a battery with the highest possible volumetric energy density. Furthermore, it is an object of the present invention to provide a method by which suitable starting materials for batteries can be produced.

  Therefore, the method described at the beginning was found.

  The method for producing the transition metal hydroxide described below is also simply referred to as the method of the present invention within the scope of the present invention.

  The method of the present invention relates to the production of transition metal hydroxides. Here, within the scope of the present invention, “transition metal hydroxide” includes not only stoichiometrically pure transition metal hydroxide, but also water in addition to transition metal ions and hydroxide ions. Also included are compounds that also have anions (eg, oxide ions, carbonate ions) that are different from oxide ions and / or cations (particularly alkali metal ions) that are different from transition metal ions. Preferred alkali metal ions are potassium and in particular sodium ions. Here, the molar ratio of the anion (different from the hydroxide ion) and the cation (different from the transition metal ion) need not be the same.

  In one embodiment of the invention, the transition metal hydroxide is in particular 0.01-55 mol%, preferably 0.2-50 mol% (hydroxide ions), based on the total number of anions. Has an anion). A preferred anion, which is different from the hydroxide ion, is an oxide (oxide).

In one embodiment of the present invention, the transition metal hydroxide is 0.01 to 10 mol%, preferably 0.2 to 6.0 mol% (transition metal ion, based on the content of the transition metal cation. Has a cation). A preferred cation that is different from the transition metal is Al ³⁺ .

  In one embodiment of the invention, the transition metal hydroxide is an oxyhydroxide in which no anion X or carbonate is detected.

  In one embodiment of the present invention, the transition metal is Cr, V, Mn, Ni, Fe, Co, Zn, Ti, Zr and a mixture of one or more of those described above, or an alkali metal, aluminum, or magnesium. Selected from a mixture, preferably from a mixture of Ni, Mn, Co, and optionally one or more further metals selected from alkali metals, aluminum and magnesium.

In one embodiment of the invention, the transition metal hydroxide has the general formula (I)
_{Ni a Mn b M c O x} (OH) y X w (CO 3) t (I)
(However, the symbols are defined as follows:
M is Co or a combination of Co and at least one element selected from Zn, Cu, Ti, Zr, Al and Mg;
X is selected from halides such as bromides, preferably chloride, more preferably fluoride, furthermore sulfates, nitrates or carboxylates, preferably C ₁ -C ₇ -carboxylates, especially benzoates or acetates;
a is a number in the range of 0.15 to 0.8, preferably in the range of 0.18 to 0.52.
b is a number in the range of 0.1 to 0.8, preferably in the range of 0.2 to 0.7;
c is a number in the range of 0.02 to 0.5, preferably in the range of 0.05 to 0.35;
Where a + b + c = 1.0,
0 ≦ w ≦ 0.3, preferably 0.001 <w <0.01,
0 ≦ x <1, preferably 0.3 <x <1,
1 <y ≦ 2, preferably 1 <y <1.7,
(0 ≦ t ≦ 0.3)
It corresponds to.

  In one preferred embodiment, X = sulfate and w = 0.005.

  The process according to the invention is carried out in a stirred vessel, for example in a stirred tank that is operated discontinuously (batch) or continuously. Here, the agitation tank can have add-ons (additives), internal structures, and / or additions (additives).

  Within the scope of the present invention, an aqueous solution of at least one transition metal salt is simplified and is also referred to as an aqueous solution of a transition metal salt.

  The aqueous solution of the transition metal salt can contain at least one transition metal salt, preferably two or three transition metals, in particular two or three transition metal salts. Particularly suitable as transition metal salts are water-soluble salts of transition metals (including multiple cases), ie having a solubility (measured at room temperature) of at least 25 g / l in distilled water, preferably at least A salt having a solubility of 50 g / l is suitable. Preferred transition metal salts, in particular nickel, cobalt and manganese salts are, for example, transition metal carboxylates, in particular acetates, in addition sulfates, nitrates, halides, in particular bromides, chlorides, in which transition metals (in the case of several types) Also preferably exists in an oxidation state of +2. Such a solution preferably has a pH value in the range 2-7, particularly preferably in the range 2.5-6.

  As the transition metal, for example, a transition metal in the first period is suitable, and zirconium and molybdenum are suitable. Preferably, Cr, V, Ni, Mn, Co, Fe, Zn, Zr, Cr and Ti are used. Preferably, a mixture of at least two transition metals as described above is selected, particularly preferably a mixture of at least three or at least two transition metals as described above and magnesium, aluminum or calcium.

  In one embodiment of the invention, the transition metal is selected from Cr, V, Ni, Mn, Co, Fe, Zn, Zr, Cr and Ti, and mixtures of one or more of the above transition metals, and particularly preferred. Is selected from a mixture of at least three or at least two of the above transition metals and magnesium, aluminum or calcium.

  In one embodiment of the invention, the transition metal is selected as a combination of Ni, Mn and Co.

  In one embodiment of the present invention, an aqueous solution of a transition metal (including a plurality of types) (in addition to water, the aqueous solution contains one or more organic solvents such as ethanol, methanol, or isopropanol with respect to water. For example, 15 volume% or less). In another embodiment of the present invention, an aqueous solution of a transition metal salt (including a plurality of types) (the aqueous solution contains an organic solvent in an amount of less than 0.1% by weight (% by weight) based on water). Or preferably free of organic solvents).

  In one embodiment of the invention, the aqueous solution of the transition metal (including multiple types) used comprises ammonia, an ammonium salt, or one or more organic amines such as methylamine or ethylenediamine. Ammonia or organic amines can be added separately or they can be formed in an aqueous solution by dissociation (splitting) of a complex salt of a transition metal salt. Preferably, the aqueous solution of the transition metal (including a plurality of types) contains less than 10 mol% of annia or organic amine with respect to the transition metal M. In a particularly preferred embodiment of the invention, the aqueous transition metal solution does not contain measurable proportions of ammonia or organic amines.

  Preferred ammonia salts may be, for example, ammonium sulfate and ammonium sulfite.

  For example, the transition metal salt aqueous solution may have a total transition metal concentration in the range of 0.01 to 5 mol / l solution, preferably 1 to 3 mol / l solution.

  In one embodiment of the invention, the molar proportion of transition metal in the aqueous solution of the transition metal salt is adapted to the desired stoichiometry of the cathode material, or transition metal mixed oxide. Here, it is considered in some cases that various transition metal carbonates have different solubilities.

  In addition to the counter ion of the transition metal salt (one or more), the aqueous solution of the transition metal can contain one or more additional salts. Here, the salt preferably does not form a (slightly) insoluble salt with M, or, for example, sodium, potassium, magnesium, or calcium bicarbonate (which can form a carbonate precipitate when the pH changes) Salt.

  In other embodiments of the present invention, the aqueous solution of one or more transition metal salts does not contain additional salts.

  In one embodiment of the present invention, the aqueous transition metal solution can include one or more additives such as biocides, complexing agents such as ammonia, chelating agents, surfactants, carboxylic acids, and buffers. . In another embodiment of the invention, the aqueous solution of the transition metal salt does not contain an additive.

  Examples of suitable reducing agents that can be present in an aqueous solution of a transition metal salt include sulfite, particularly sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium bisulphite, ammonium sulfite, and hydrazine, and Salts of hydrazine such as hadrogen sulfate, and further water-soluble organic reducing agents such as ascorbic acid or aldevid.

  For example, it may be combined with an aqueous solution of at least one alkali metal hydroxide by adding an alkali metal hydroxide solution to an aqueous solution of a transition metal salt. Particularly preferred alkali metal hydroxides (alkali metal hydroxides) are sodium hydroxide and potassium hydroxide.

  In one embodiment of the invention, precipitation is performed by adding an aqueous solution of sodium hydroxide or potassium hydroxide to an aqueous solution of transition metal acetate, sulfate, or nitrate.

  The aqueous solution of alkali metal hydroxide can have a hydroxide concentration of 0.1 to 3 mol / l, preferably 1 to 2.5 mol / l.

The aqueous solution of alkali metal hydroxide can contain one or more further salts, for example ammonium salts, in particular ammonium hydroxide, ammonium sulfate or ammonium sulfite. In one embodiment, the molar ratio NH ₃ : transition metal can be set to 0.01 to 0.9, particularly preferably 0.08 to 0.65.

  In one embodiment of the present invention, the alkali metal hydroxide aqueous solution may comprise ammonia or one or more organic amines, such as melamine.

  In other embodiments of the invention, one or more ammonium salts, ammonia, or one or more organic amines can be added separately to the reaction mixture.

  This combination can be performed continuously or discontinuously in one or more steps. Via one or more supply points, a solution of alkali metal hydroxide can be supplied to the stirring vessel, and each supply point can be provided above or below the liquid level. In particular, it can be metered (exactly) into the vortex (of the stirring tank) formed by the stirrer. Thus, further, an aqueous solution of the transition metal salt can be metered into the stirring vessel via one or more supply points (specific supply points are provided above or below the liquid level). . In particular, it can be accurately metered into the vortex (of the stirring tank) formed by the stirrer.

  In one embodiment of the present invention, an alkali metal hydroxide solution is fed into a stirring vessel through separate feed points together with a plurality of one kind of transition metal salt aqueous solution. Is done. In other embodiments of the present invention, the integration (combination) comprises each of a solution of alkali metal hydroxide, together with an aqueous solution containing all the desired transition metals as salts for performing the method of the present invention. It is carried out by supplying the stirring vessel through a separate supply point. The latter procedure has the advantage that non-uniformity in the concentration ratios of various transition metals can be easily prevented.

  By integrating an aqueous solution of the transition metal salt and a solution of at least one alkali metal hydroxide, an aqueous suspension of the transition metal hydroxide is obtained, where the transition metal hydroxide precipitates. Here, the aqueous continuous phase, also referred to as mother liquor within the scope of the present invention, comprises a water-soluble salt and optionally further additives present in the solution. Examples of water-soluble salts include alkali metal salts of the transition metal of interest, such as sodium acetate, potassium acetate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, sodium halide, potassium halide. Illustrative and include the corresponding ammonium salts such as ammonium nitrate, ammonium sulfate, and / or ammonium halide. Most preferably, the mother liquor contains sodium chloride, potassium chloride, or ammonium chloride. Furthermore, the mother liquor can additionally contain salts, optionally (introduced) additives, and excess alkali metal hydroxides, and can further contain transition metals that do not precipitate as transition metal salts.

  The pH value of the mother liquor is preferably in the range of 9 to 12.7, particularly preferably in the range of 10.5 to 12.2 (measured after the mother liquor has been cooled to 23 ° C.).

  It has been found that the morphology and surface properties of the transition metal mixture can affect not only the calcination process but also the process of producing the precursor. Here, it was found that the morphology can be controlled by introducing a mechanical output with a large value. It is mechanically difficult to put a larger value of mechanical energy into a larger volume. In order to overcome such difficulties, in at least one further section, a part of the suspension is in the range of 50-10000 W / l (relative to the part of the suspension), preferably 200 A mechanical power of ˜2500 W / l (watts per liter) is continuously introduced and then the part is returned to the stirred vessel.

  In one embodiment of the invention, the power density introduced into the further section, and thus the power per unit volume, is about 50 to 100 times higher than in the stirred vessel.

  Here, as individual sections, pumps, inserts, mixing units, wet mills, stirring tanks, and homogenizers can be selected, where the stirring tanks selected as further sections are preferably as described above. Having a volume that is clearly smaller than the volume of the stirred vessel.

  Examples of particularly preferred pumps are centrifugal pumps and peripheral wheel pumps.

  As separate sections, separate containers can be used, or inserts in stirred containers can be used. Here, the insert is understood to be a piece of equipment that exists within the volume of the original stirring vessel, but is partitioned and has its own mixing unit. For example, as an insert, one can choose a tube that is present in a stirred vessel and immersed in the reaction mixture and stirred using a further stirrer, for example a stirrer with a propeller. Thereby, a division is formed in the stirring vessel. The ratio of the divided volume to the total volume is 0.01 to 15% by volume, preferably 0.1 to 10% by volume. In one variation, there are a plurality of such segments, which may have the same or different sizes.

  Here, “introducing (giving)” continuously refers to a plurality of small volumes of the generated suspension during the precipitation, at shorter intervals, or continuously with a predetermined partial stream of the generated suspension. , Understood to mean removing from the stirring vessel, introducing mixing energy and then returning the part back to the stirring vessel.

  The introduction of mechanical energy into the stirring tank can be performed, for example, by vigorous stirring. Such agitation is much simpler than in a (large) agitation vessel.

  In a variant of the invention, the mechanical energy can be introduced at least partly by ultrasound.

Here, for example, in the case of a stirring tank, the small volume can be 0.1 to 10% of the stirring container described above, whereas in the case of a pump or a wet mill (wet grinder), It can be as small as 0.01 to 0.0099%.
In one embodiment of the invention, a separate vessel is installed in the agitation vessel, for example it is coupled to the agitation vessel by a pump circulation system. In another embodiment of the present invention, the agitation vessel is comprised of two or more separate vessels (which are coupled to the agitation vessel by one or more pump circulation systems).

  The “pump circulation system” is preferably a device that continuously removes a portion of the reactor from the reactor, introduces it into a separate container, and flows it back into the separate container before returning it to the reactor again. It is understood that. Here, a pump is used to maintain the flow. In certain embodiments, the device residing in a separate container has a pumping action, which allows it to operate without a separate pump unit.

  In one embodiment of the invention, when carrying out the method of the invention, an average power in the range of 2-25 W / l, preferably in the range of 3-17 W / l, is applied to the total suspension.

  In one embodiment of the invention, 20-80% of the mechanical output, preferably at least 30%, particularly preferably at least 40% of the mechanical output is put into the further section.

  In one embodiment of the invention, the process according to the invention is carried out in a temperature range of 20-90 ° C., preferably in a temperature range of 30-80 ° C., particularly preferably in a temperature range of 35-75 ° C. Here, the temperature in the stirring vessel is measured. The temperature in one or more further containers can be different from the temperature in the stirred container.

The process according to the invention can be carried out under air, under an inert atmosphere, for example under a noble gas- or nitrogen atmosphere, or under a reducing atmosphere. Examples of reducing gas include CO and SO ₂ . It is preferable to carry out in an inert atmosphere.

  The process according to the invention can be carried out at any pressure as long as it does not fall below the vapor pressure of the aqueous solution and suspension. Suitable are, for example, 1 to 10 bar, preferably standard pressure.

  In one embodiment of the present invention, the average solid content is measured in a stirred vessel to a range of 70 to 1000 g / l, preferably 80 to 500 g / l.

  In one embodiment of the invention, the average residence time in the stirring vessel is treated in the range of 2-18 hours, preferably in the range of 4-14 hours.

  In one embodiment of the invention, the average residence time in the container is treated in the range of 0.01 to 0.5 seconds, preferably in the range of 0.2 seconds.

  In one embodiment of the invention, the average residence time in the further vessel is less than one thousandth of the average residence time in the stirred vessel, but at least one millionth.

  The process according to the invention can be carried out in steady state or unsteady state, where steady state is preferred.

  With transition metal hydroxides produced according to the process according to the invention, very good morphology is obtained. That is, it has an average particle size (D50) of 6-12 μm, preferably 7-12 μm. Here, the average particle size (D50) represents the median value of the volume-based particle size (as can be determined, for example, by light scattering) within the scope of the present invention.

  In one embodiment of the invention, the precipitated transition metal hydroxide is separated from the mother liquor. The concept of “mother liquor” has been explained previously.

  When the separation is carried out continuously, a representative or non-representative part of the resulting suspension can be removed from the reaction vessel, for example, in a fixed amount. Thus, for example, it is possible to remove the separated mother liquor or transition metal hydroxide in the course of removal from the reaction vessel. In taking out from the reaction vessel, a transition metal hydroxide having a predetermined particle diameter can be taken out, which is preferable. Both latter embodiments usually apply to conducting the reaction in a non-steady state mode.

  Separation is performed, for example, by filtration, centrifugal force, decantation, spray drying, or precipitation, or by a combination of two or more of the operations described above. For example, a filter press, a belt filter, a hydrocyclone, an inclined plate purifier, or a combination of the above devices is suitable as the device.

  In the separation, particularly when the separation is performed by filtration, one or more washing steps can be performed later. For example, washing with pure water or with an aqueous solution of alkali metal carbonate or alkali metal hydroxide, in particular with an aqueous solution of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia be able to. Water is preferred.

  The washing step can be performed, for example, at 30 to 50 ° C. by increasing the pressure or increasing the temperature. In another variation, one or more cleaning steps are performed at room temperature.

  The efficiency of the washing process can be examined by analytical processing. For example, the content of the transition metal M in the wash water can be analyzed.

  When washing is performed using water instead of an aqueous solution of alkali metal carbonate, it is possible to examine whether or not water-soluble substances such as water-soluble salts can be washed and removed using a conductivity test of the washing water.

  In the separation, one or more drying steps can be performed later. The drying step can be performed at room temperature or at a higher temperature. For example, it can be dried at a temperature of 30 to 150 ° C.

  The drying step can be carried out at standard pressure or under reduced pressure, for example at a pressure in the range of 10 mbar to 500 mbar.

  In one embodiment of the invention, the drying is performed under air.

  In one embodiment of the invention, the precursor produced by the method according to the invention still contains physically bound water after one or more optional drying steps.

  In one embodiment of the invention, after the separation, one or more cleaning steps and optionally one or more drying steps are performed.

  The water content and particle size of the transition metal mixed oxide precursor are measured after separation of the mother liquor, preferably after drying.

  In one embodiment of the present invention, transition metal hydroxide particles having a diameter greater than 20 μm are separated, for example, by sieving. If sieving is desired, sieving is preferably performed after drying. Preferably, particles of transition metal hydroxide with a diameter of more than 32 μm, particularly preferably more than 50 μm, are separated.

  According to the process according to the invention, the transition metal hydroxide can be obtained in particulate form, which is also referred to simply as precursor. The precursors produced by the method according to the invention are very suitable for the production of electrode materials for cathodes for lithium ion batteries.

  A further object of the present invention is a particulate transition metal water comprising at least one transition metal hydroxide selected from the hydroxides of Cr, V, Mn, Ni, Fe, Co, Zn, Ti and Zr. The oxide is essentially spherical, the part of the particles having a diameter of more than 50 μm is less than 0.1% by mass, the average diameter (D50) is in the range of 6-12 μm, and the tamp density is at least ( 1.95 + 0.03 · (D50) / μm) kg / l. Such particulate transition metal hydroxides are also referred to simply as transition metal hydroxides according to the present invention within the scope of the present invention.

  In one embodiment of the invention, the transition metal is Cr, V, Mn, Ni, Fe, Co, Zn, Ti, Zr and a mixture of one or more of the foregoing, or an alkali metal, aluminum, or magnesium. Selected from a mixture, preferably selected from a mixture of Ni, Mn, Co and optionally one or more further metals (selected from alkali metals, aluminum and magnesium).

In one embodiment of the invention, the transition metal hydroxide has the general formula (I)
_{Ni a Mn b M c O x} (OH) y X w (CO 3) t (I)
(However, the symbols are defined as follows:
M is Co or a combination of Co and at least one element selected from Zn, Cu, Ti, Zr, Al and Mg;
X is selected from halides such as bromides, preferably chlorides, particularly preferably fluorides, furthermore sulfates, nitrates or carboxylates, preferably C ₁ -C ₇ -carboxylates, in particular benzoates or acetates,
a is a number in the range of 0.15 to 0.8, preferably a number in the range of 0.18 to 0.52.
b is a number in the range of 0.1 to 0.8, preferably a number in the range of 0.2 to 0.7;
c is a number in the range of 0.02 to 0.5, preferably a number in the range of 0.05 to 0.35;
Where a + b + c = 1.0,
0 ≦ w ≦ 0.3, preferably 0.001 ≦ w ≦ 0.01,
0 ≦ x <1, preferably 0.3 <x <1,
1 <y ≦ 2, preferably 1 <y <1.7,
(0 ≦ t ≦ 0.3)
It corresponds to.

  In one preferred embodiment, X = sulfate and w = 0.005.

  The transition metal hydroxide according to the invention is basically spherical. This is understood to mean that the transition metal hydroxide particles are essentially spherical in shape.

  Preferably, the transition metal hydroxide according to the invention comprises at least two different transition metals and in particular as cations, in particular as cations with an oxidation state of +2. Particularly preferably, the transition metal hydroxides according to the invention comprise a mixture of Ni, Mn, Co and in particular as cations, in particular as cations with an oxidation state of +2, and optionally alkali metals, aluminum and magnesium One or more further metals selected from:

  Here, “basically spherical” includes those that are not strictly spherical, and also includes, for example, elliptical shapes that differ by a maximum of 10% between the major axis and the minor axis. The morphology of the transition metal hydroxide is determined by microscopy, for example by light microscopy (LMI) or operational electron microscopy (SEM).

  Here, “basically spherical” includes those in a typical sample that are not strictly spherical (at least 95% (mass average) of the particles are basically spherical in content).

  The particle diameter (D50) of the transition metal hydroxide according to the invention is in the range 2 to 25 μm, preferably in the range 7 to 16 μm and particularly preferably 12 μm or less. Here, within the scope of the present invention, the particle diameter (D50) represents the average particle diameter (mass average), which is determined, for example, by light scattering.

  In the transition metal hydroxide according to the present invention, the proportion of particles having a diameter of more than 50 μm is less than 0.1 mass% (wt%), preferably 0.001 to 0.05 mass%.

  In the transition metal hydroxide according to the invention, the part of the particles with a diameter larger than 32 μm is preferably less than 0.1% by weight, preferably 0.001 to 0.05% by weight (% by weight).

  In the transition metal hydroxide according to the invention, the part of the particles with a diameter larger than 20 μm is particularly preferably less than 0.1% by weight, preferably 0.001 to 0.05% by weight (% by weight).

  In one embodiment of the invention, the transition metal hydroxide particles according to the invention have a diameter (D99) of up to 50 μm, preferably up to 32 μm, and particularly preferably measured as volume- or mass average. The maximum is 20 μm.

  In one embodiment of the present invention, the transition metal hydroxide according to the present invention has a very small amount of fine powder, for example, particles having a diameter of less than 1 μm are less than 2% by mass.

  The transition metal hydroxide according to the invention has a tam density of at least (1.95 + 0.03 · (D50) / μm) kg / l.

  In one embodiment of the invention, the transition metal hydroxide according to the invention has a maximum tamped density of (2.30 + 0.03 · (D50) / μm) kg / l.

  The tamp density can be measured, for example, basically according to DIN 53194 or DIN ISO 787-11, but is advantageously below 1250 impact and has a smaller cylinder.

  In one embodiment of the present invention, the transition metal cation is dispersed in the transition metal hydroxide particles according to the present invention without forming a domain (exclusive region). Various domains are detected, for example, by electron beam-microanalysis (EPMA, Electron Probe X-ray Microanalysis in English).

  In one embodiment of the invention, the sample of transition metal hydroxide according to the invention has a uniform (uniform) composition. This is understood to mean that the composition of the individual particles does not deviate by more than 15 mol% (relative to the respective transition metal content) from the average value of the sample.

  The transition metal oxides according to the invention can be processed well into transition metal mixed oxides, which can be used for the production of lithium ion battery electrodes. A further subject of the present invention is a method of using the transition metal hydroxide according to the present invention for the production of transition metal mixed oxides. A further object is a process for producing transition metal mixed oxides using the transition metal hydroxide according to the invention.

  In order to produce a transition metal mixed oxide, a mixture of at least one transition metal hydroxide according to the present invention and at least one lithium compound is heat treated at a temperature in the range of 600-1000 ° C. be able to.

Suitable lithium compounds are, for example, organometallic and preferably inorganic metal lithium compounds. Particularly preferred organolithium compounds are selected from LiOH, Li ₂ CO ₃ , Li ₂ O and LiNO ₃ and the corresponding hydrates such as LiOH.H ₂ O. For mixing, for example, the transition metal hydroxide according to the invention can be mixed with the lithium compound and processed in a solid mixer.

  In one embodiment of the invention, the transition metal hydroxide and lithium compound mixture according to the invention sets the stoichiometric amount of the transition metal mixed oxide, in particular the molar ratio of lithium to the total of transition metals. Is set to be in the range of 0.9 to 1.6, preferably in the range of 1 to 1.25, and particularly preferably in the range of 1.1. In other embodiments, the stoichiometric amount is set so that the molar ratio of lithium to the total of transition metals is about 0.5, for example in the range of 0.4 to 0.6. Can do.

  In one embodiment, the stoichiometric amount is set such that the molar ratio of lithium to the total of transition metals is about 1.4, which can range, for example, from 1.28 to 1.52. it can.

  The transition metal mixed oxides produced according to the invention are very good to process (for example due to their good fluidity) and under the use of the transition metal mixed oxides produced according to the invention In addition, when an electrochemical cell is manufactured, very good hysteresis stability (cycle stability) is exhibited.

  In order to produce an electrode according to the invention, the transition metal mixed oxide can first be processed into an electrode material and processed.

  In addition to the transition metal mixed oxide, the electrode material further contains carbon in a conductive state (polymorphic state), for example, in the form of carbon black, graphite, graphene, carbon nanotube, or activated carbon.

  The electrode material further comprises at least one binder, such as a polymeric binder.

  Suitable binders are preferably selected from organic (co) polymers. Suitable (co) polymers, i.e. homopolymers or copolymers, can be selected from (co) polymers obtained, for example, by anionic, cationic or radical (co) polymerization, in particular polyethylene, polyacrylonitrile, polybutadiene, It can be selected from polystyrene and at least two copolymers selected from ethylene, propylene, styrene, (meth) acrylonitrile, and 1,3-butadiene. Polypropylene is also suitable. Furthermore, polyisoprene and polyacrylate are also suitable. Polyacrylonitrile is particularly preferred.

  With respect to polyacrylonitrile, it is understood within the scope of the present invention that it is not only a polyacrylonitrile homopolymer but also a copolymer of acrylonitrile and 1,3-butadiene or styrene. Polyacrylonitrile homopolymer is preferred.

Within the scope of the present invention, it is understood that the polyethylene is not only a homopolyethylene but also a certain copolymer of ethylene. The given copolymer here comprises at least 50 mol% of ethylene in the polymerized state and not more than 50 mol% of at least one further comonomer such as α-olefins such as propylene, butylene (1-butene), 1 -Hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, further isobutene, vinyl aromatic compounds such as styrene, further (meth) acrylic acid, vinyl acetate, vinyl propionate, (meth) acrylic acid _C 1 _{-C 10} of - alkyl esters, especially methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n- butyl acrylate, 2-ethylhexyl acrylate, n- butyl methacrylate, 2-ethylhexyl methacrylate, addition of maleic acid, maleic anhydride , And is intended to include itaconic anhydride. The polyether may be HDPE or LDPE.

  Within the scope of the present invention, polypropylene is understood to represent not only homopolypropylene but also certain copolymers of propylene. Here, the given copolymer of propylene comprises at least 50 mol% of propylene in the polymerized state and not more than 50 mol% of at least one further comonomer, such as ethylene, and an α-olefin such as butylene, 1 Includes -hexene, 1-octene, 1-decene, 1-dodecene, and 1-pentene. For polypropylene, it is preferably isotactic or essentially isotactic polypropylene.

Within the scope of the present invention, polystyrene means not only a homopolymer of styrene but also acrylonitrile, 1,3-butadiene, (meth) acrylic acid, C ₁ -C ₁₀ -alkyl esters of (meth) acrylic acid. , Divinylbenzol, in particular 1,3-divinylbenzol, 1,2-diphenylethylene, and copolymers with α-methylstyrene.

  Another preferred binder is polybutadiene.

  Other suitable binders are selected from polyethylene oxide (PEO), cellulose, carboxymethyl cellulose, polyimide and polyvinyl alcohol.

In one embodiment of the present invention, the binder has an average molar mass _{M w} of, 50000～1000000G / mols, preferably 500 000 g / mol or less in the range of (co) polymers.

  The binder can be a crosslinked or non-crosslinked (co) polymer.

  In another particularly preferred embodiment of the invention, the binder is selected from halogenated (co) polymers, in particular fluorinated (co) polymers. Here, the halogenated and fluorinated (co) polymers comprise at least one halogen atom, or at least one fluorine atom, preferably at least two halogen atoms, or at least two fluorine atoms. It is understood that it is a (co) polymer containing (co) monomer in the polymerized state.

  Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene-copolymer, vinylidene fluoride-hexafluoropropylene-copolymer (PVdF-HFP), vinylidene fluoride. Do-tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, and ethylene-chlorofluoroethylene copolymers.

  Suitable binders are in particular polyvinyl alcohols and halogenated (co) polymers such as polyvinyl chloride, or polyvinylidene chloride, in particular fluorinated (co) polymers such as polyvinyl fluoride, and in particular polyvinylidene fluoride, and polytetrafluoro. Ethylene.

  The conductive carbon-containing material can be selected from, for example, graphite, carbon black, carbon nanotubes, graphene, or a mixture of at least two of the aforementioned substances. Within the scope of the present invention, the conductive carbon-containing material is simply referred to as carbon (B).

  In one embodiment of the invention, the conductive carbon-containing material is carbon black. The carbon black can be selected from, for example, lamp black, furnace black, frame black, thermal black, acetylene black, and industrial black. Carbon black can also contain impurities, for example hydrocarbons, in particular aromatic hydrocarbons, or oxygen-containing compounds, or oxygen-containing groups, for example OH-groups. Furthermore, sulfur- or iron-containing impurities can also be included in the carbon black.

  In one variation, the conductive carbon-containing material is partially oxidized carbon black.

  In one embodiment of the present invention, the conductive carbon-containing material is carbon nanotubes (carbon nanotubes in English). Carbon nanotubes (CNT for short) are known, for example, single-wall carbon nanotubes (single-walled carbon nanotubes, SW CNT) and preferably multi-wall carbon nanotubes (multi-walled carbon nanotubes, MW CNT). is there. Regarding the manufacturing method and characteristics, for example, A. Jess et al. in Chemie Ingenieur Technik 2006, 78, 94-100.

  In one embodiment of the invention, the carbon nanotubes have a diameter in the range of 0.4 to 50 nm, preferably in the range of 1 to 25 nm.

  In one embodiment of the invention, the carbon nanotubes have a length in the range of 10 nm to 1 mm, preferably in the range of 100 nm to 500 nm.

  Carbon nanotubes can be produced by a method known per se. For example, a volatile carbon-containing compound, such as methane, or carbon monoxide, acetylene, or ethylene, or a mixture of volatile carbon-containing compounds, such as synthesis gas, with one or more reducing agents, such as hydrogen, and / or It can be decomposed in the presence of further gas, for example nitrogen gas. Another suitable gas mixture is a mixture of carbon monoxide and ethylene. Suitable temperatures for the decomposition are, for example, in the range from 400 to 1000 ° C, preferably from 500 to 800 ° C. Suitable pressure conditions for decomposition are, for example, standard pressure to 100 bar, preferably 10 bar or less.

  Single (single) or more wall carbon nanotubes can be obtained, for example, by cracking carbon-containing compounds in an arc, and this can be done in the presence or absence of cracking catalysts. .

  In one embodiment, the volatile carbon-containing compound (s) can be performed in the presence of a cracking catalyst such as Fe, Co or preferably Ni.

  Graphene is understood to be a nearly ideal or ideal two-dimensional hexagonal carbon crystal within the scope of the present invention and is constructed similar to individual graphite layers.

  In one embodiment of the present invention, the mass ratio of the transition metal mixed oxide modified according to the present invention and the conductive carbon-containing material is 200: 1 to 5: 1, preferably 100: 1 to 10: 1. It is a range.

  A further aspect of the invention is an electrode comprising at least one transition metal mixture prepared as described above, at least one conductive carbon-containing material, and at least one binder.

  The transition metal mixed oxide and the conductive carbon-containing material have been described above.

  A further subject of the present invention is an electrochemical cell (electrochemical cell) which is produced using at least one electrode according to the invention. A further subject of the present invention is an electrochemical cell comprising at least one electrode according to the invention.

In one embodiment of the present invention, the electrode material produced according to the present invention includes:
60-98 mass% (wt%), preferably 70-96 mass% transition gold blue mixed oxide,
1-20% by weight, preferably 2-15% by weight binder,
1 to 25% by mass, preferably 2 to 20% by mass of a conductive carbon-containing material.

  The geometry of the electrode material according to the invention can be selected within a wide range. Preferably, the electrode according to the invention can be formed into a thin film, for example a film with a thickness in the range of 10 μm to 250 μm, preferably in the range of 20 to 130 μm.

  In one embodiment of the invention, the electrode according to the invention is a foil, for example a metal foil, in particular an aluminum foil, or a polymer foil, for example a polyester foil, which may be untreated or siliconized. May be included).

  A further subject of the present invention is a method of using an electrode material according to the invention or an electrode according to the invention in an electrochemical cell. A further subject of the present invention is a method for producing an electrochemical cell using an electrode material according to the invention or an electrode according to the invention. A further subject of the present invention is an electrochemical cell comprising at least one electrode material according to the invention, or at least one electrode according to the invention.

  The electrode according to the invention acts as cathode (according to definition) in an electrochemical cell according to the invention. An electrochemical cell according to the present invention comprises a counter electrode defined as an anode within the scope of the present invention, and this is for example a carbon-anode, in particular a graphite-anode, a lithium-anode, a silicon-anode, or a lithium-titanate- It can be an anode.

  The electrochemical cell according to the invention can be, for example, a battery or a storage battery (secondary battery).

  In addition to the anode and the electrode according to the invention, the electrochemical cell according to the invention consists of further components, for example, conductive salts, non-aqueous solvents, separators, output conductors, such as metals or alloys. , And cable connections and housings.

  In one embodiment of the invention, an electrical cell according to the invention. Comprising at least one non-aqueous solvent, which can be liquid or solid at room temperature, and preferably is a polymer, cyclic or acyclic ether, cyclic and acyclic acetal, and cyclic Alternatively, it is selected from acyclic organic carbonates.

Examples of suitable polymers are in particular polyalkylene glycols, preferably poly-C ₁ -C ₄ -alkylene glycols, and in particular polyethylene glycol. Here, polyethylene glycol can be contained in a state in which 20 mol% or less of one or more C ₁ -C ₄ -alkylene glycols are polymerized. Here, the polyalkylene glycol is preferably a polyalkylene glycol in which methyl or ethyl is double-bonded.

  Suitable polyalkylene glycols, and particularly suitable polyalkylene glycols, have a molecular weight of at least 400 g / mol.

The molecular weight _Mw of suitable polyalkylene glycols and particularly suitable polyethylene glycols is 5000000 g / mol or less, preferably 2000000 g / mol or less.

  Examples of suitable acyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, preferably 1,2-dimethoxyethane.

  Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.

  Examples of suitable acyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane, and 1,1-diethoxyethane.

  Examples of suitable cyclic acetals are 1,3-dioxane, and in particular 1,3-dioxolane.

  Examples of suitable acyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate.

  Examples of suitable cyclic organic carbonates are general formulas (II) and (III)

Wherein R ¹ , R ² and R ³ can be the same or different and are hydrogen and C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl , N-butyl, iso-butyl, sec-butyl, and tert-butyl, wherein preferably R ² and R ³ are not both tert-butyl.

In one particularly preferred embodiment, R ¹ is methyl and R ² and R ³ are each hydrogen, or R ¹ , R ² and R ³ are each hydrogen.

  Another preferred cyclic organic carbonate is vinylene carbonate, formula (IV).

  Preferably, one or more solvents are used in the so-called anhydrous state, i.e. in a state where the water content is in the range from 1 ppm to 0.1% by weight (determined by Karl Fischer titration).

The electrochemical cell according to the invention further comprises at least one conductive salt. Suitable salts are in particular lithium salts. Examples of suitable lithium salts are LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiC (C _n F _{2n + 1} SO ₂ ) ₃ , lithium imide, for example LiN (C _n F _{2n + 1} SO ₂ ) ₂ (where n is an integer in the range of 1-20), LiN (SO ₂ F) ₂ , Li ₂ SiF ₆ , LiSbF ₆ , LiAlCl ₄ , and the general formula (C _n F _{2n + 1} SO ₂ ) _t YLi Where t is defined as follows:
When Y is selected from oxygen or sulfur, t = 1,
When Y is selected from nitrogen and phosphorus, t = 2,
T = 3 when Y is selected from carbon and silicon.

Preferred conductive salts are selected from LiC (CF ₃ SO ₂ ) ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiPF ₆ , LiBF ₄ , LiClO ₄ , and particularly preferably LiPF ₆ and LiN (CF ₃ SO ₂ ). Selected from ₂ .

  In one embodiment of the invention, an electrochemical cell according to the invention comprises one or more separators (by which the plurality of electrodes are mechanically separated). Suitable separators are polymer films that are non-reactive with lithium, especially porous polymer films. Particularly suitable materials for the separator are polyolefins, in particular film-like porous polyethylene, and film-like porous polypropylene.

  Polyolefin separators, particularly polyethylene or polypropylene separators, can have a porosity in the range of 35-45%. A suitable pore size is, for example, in the range of 30 to 500 nm.

  In other embodiments of the invention, the separator can be selected from PET nonwovens filled with inorganic particles. Such a separator can have a porosity of 40-55%. A suitable pore size is, for example, in the range of 80 to 750 nm.

  The electrochemical cell according to the present invention further comprises a housing, which can have any shape, for example a cubic or cylindrical sheet. In one variant, the housing is a metal foil made as a pouch.

  The electrochemical cell according to the present invention provides a high voltage and has a high energy density and good stability.

  The electrochemical cells according to the invention can be combined with each other, for example connected in series or in parallel. A series connection is preferred.

  A further subject of the present invention is a method of using an electrochemical cell according to the invention in a device, in particular a mobile device. Examples of mobile devices are vehicles, such as cars, bicycles, aircraft, or water equipment, such as boats, ships. Other examples for mobile devices (mobile devices) are those that are operated by oneself, eg computers, especially laptops, telephones or electrical manual tools, eg those in the construction field, especially boring equipment, electric field type It is a drill or a scraper.

  Use of the electrochemical cell according to the present invention in equipment (units) provides a longer run time before recharging. If an electrochemical cell tries to get the same matter time with less energy density, the heavier weight (mass) of the electrochemical cell must be used.

  The present invention will be described below using examples.

  Examples and comparative examples were carried out in a reactor system with a total volume of 6 l. Here, the reactor system has a stirring tank having a volume of 5.7 l and has an assembly which has a volume arranged in the pump circulation system (pump internal volume) of 0.04 l. The rotary pump (centrifugal pump) was used, and the assembly including this was 0.3 l in volume.

  The assembly can provide up to 45 W mechanical work in suspension. The assembly can carry liquid and maintain a volumetric flow of 1200 l / h. In the stirring tank, a mechanical stirring output of 30 W was measured. The average residence time in the stirring tank was 10 hours.

  Calculated from the volume flow and total volume, it was found that the suspension was exposed to mechanical stress in the assembly every 18 s on average (1/2000 of the average residence time). The power introduction in the assembly was calculated to be 1125 W / l. The suspension residence time in the assembly averaged 120 ms (milliseconds). The mechanical power introduction was 12.5 W / l for the entire system.

  The reactor system was equipped with a pitched blade stirrer and baffle. The stirring output was measured by measuring the rotational moment composed of the rotational speed and the rotational moment using an electric motor. Furthermore, the reactor system was equipped with a plurality of metering introduction units and further overflows (through which the reaction mixture was taken out), said metering introduction unit having a metering introduction pump.

The following solutions were used:
Solution A: 0.55 moles of nickel sulfate, cobalt sulfate, and manganese sulfate per kg of solution (this is as a sulfate and is made by dissolving the corresponding hydrate complex in water).

Solution B: Contains 4.4 mol NaOH per kg solution and 1.3 mol NH ₃ per kg solution. Prepared by diluting 50% NaOH and 25% ammonia solution with water.

  Solution C: 4.4 mol NaOH per kg solution.

  Metering was performed using a metering pump.

1. Example 1 according to the invention
The reactor system was purged with 40 Nl / h nitrogen (standard liters). Then, using a metering pump, solutions A and B are metered into the turbulent region (near the stirring blade of the reactor system stirring tank) at a constant metering flow (30 g / h and 200 g / h). did. Using a regulator, the pH value was kept constant at 11.3 by adding solution C. This formed a suspension. The temperature of the suspension was set at 45 ° C. The pH value was set to 11.3 by adding solution C (measured at 23 ° C.). The average residence time of the suspension in the reactor system was 15 seconds. After 3 days, a steady state was reached.

  The stirrer output was 40W and the power introduced into the assembly was 45W. The flow rate in the assembly was 1200 l / h.

A suspension of transition metal hydroxide with a molar ratio of Ni: Co: Mn of 33:34:33 was obtained. The transition metal hydroxide suspension obtained from the overflow is filtered through a suction filter, the filter cake is washed with water, 3% by weight NaOH, and again with water, and Dry at 105 ° C. for 12 hours. The transition metal hydroxide TM. 1 (21.2% Ni; 22.1% Co; 20.3% Mn; Formula Ni _0.33 Co _0.34 Mn _0.33 (OH) _1.17 O _0.83 (SO ₄ ) _0.003 ) Was sieved (mesh width 50 μm) and the tamp density was measured.

In order to measure the tamped density in the electrode material, the transition metal hydroxide TM. A predetermined proportion of 1 was mixed with lithium carbonate and heat treated at 900 ° C. For this purpose, 41.18 g of lithium carbonate (99.6% LiCO ₃ , sieving, 100% <50 μm) were combined with 90.35 g of transition metal hydroxide TM. 1 and mixed in a ball mill, introduced into a crucible and calcined in a muffle furnace (107 minutes heated to 350 ° C., 4 hours maintained, 107 minutes heated to 675 ° C., 4 hours maintained, 75 minutes 900 ° C. Heated to 6 hours; and cooled to room temperature in an oven). The resulting material was sieved to <32 μm and the tamped density was measured.

2. Comparative Example C-2
The procedure was performed as described in 1 except that the assembly and pump circulation system were closed.

  A suspension of transition metal hydroxide with a molar ratio of Ni: Co: Mn of 33:34:33 was obtained. The transition metal hydroxide suspension obtained from the overflow is filtered through a suction filter, the filter cake is washed with water, 3% by weight NaOH, and again with water, and Dry at 105 ° C. for 12 hours. The transition metal hydroxide C-TM. 2 (22.2% Ni; 22.2% Co; 20.0% Mn) was sieved (mesh width 50 μm) and the tamp density was measured.

In order to measure the tamped density in the electrode material (cathode material), the transition metal hydroxide C-TM. A predetermined proportion of 2 was mixed with lithium carbonate and heat treated at 900 ° C. For this purpose, 41.26 g of lithium carbonate (99.4% LiCO ₃ , sieving, 100% <50 μm) were combined with 89.23 g of transition metal hydroxide C-TM. 2 in a ball mill, introduced into a crucible and calcined (107 minutes heated to 350 ° C., 4 hours maintained, 107 minutes heated to 675 ° C., 4 hours maintained, 75 minutes heated to 900 ° C., 6 Time maintained; and cooled to room temperature in furnace). The resulting material was sieved to <32 μm and the tamped density was measured.

3. Comparative Example C-3
The procedure was performed as described in 1 except that a smaller assembly with a volume of 0.015 l was chosen. The flow rate in the assembly was 300 l / h. This introduced only 8W / 53W, i.e. 15% of the mechanical power, into the section and at a higher power density.

A suspension of transition metal hydroxide with a molar ratio of Ni: Co: Mn of 33:34:33 was obtained. The transition metal hydroxide suspension obtained from the overflow is filtered through a suction filter, the filter cake is washed with water, 3% by weight NaOH, and again with water, and Dry at 105 ° C. for 12 hours. The transition metal hydroxide C-TM. 3 (21.6% Ni; 22.1% Co; 19.8% Mn; Formula Ni _0.33 Co _0.34 Mn _0.33 (OH) _1.14 O _0.86 (SO ₄ ) _0.003 ) Was sieved (mesh width 50 μm) and the tamp density was measured.

In order to measure the tamped density in the electrode material (cathode material), the transition metal hydroxide C-TM. A predetermined proportion of 3 was mixed with lithium carbonate and heat treated at 900 ° C. For this purpose, 41.26 g of lithium carbonate (99.4% LiCO ₃ , sieving, 100% <50 μm) were replaced with 90.64 g of transition metal hydroxide C-TM. 3 in a ball mill, introduced into a crucible and calcined (107 minutes heated to 350 ° C., 4 hours maintained, 107 minutes heated to 675 ° C., 4 hours maintained, 75 minutes heated to 900 ° C., 6 Time maintained; and cooled to room temperature in furnace). The resulting material was sieved to <32 μm and the tamped density was measured.

  TD: tamped density, measured using tamped volumetric meter STAV II (2000 taps from Engelsmann, Ludwigshafen).

Claims (10)

A method for producing a transition metal hydroxide having an average particle size in the range of 6 to 12 μm (D50),
In a predetermined stirred vessel, at least one solution of at least one transition metal salt and at least one solution of at least one alkali metal hydroxide are combined, and thereby the transition metal hydroxide An aqueous suspension is produced, and within at least one separate section, a portion of the suspension, each with continuous mechanical power in the range of 50-10000 W / l for a portion of the suspension And then returning the part to the stirring vessel.   The transition metal is selected from Cr, V, Mn, Ni, Fe, Co, Zn and a mixture of one or more of them or a mixture of one or more of these with an alkali metal, aluminum, or magnesium. The method according to claim 1.   3. The method according to claim 1, wherein a total average power of 2 to 25 W / l is provided for the entire suspension.   4. A method according to any one of claims 1 to 3, characterized in that at least 20% of the total mechanical power introduced is provided at a power density of 50 to 10000 W / l.   5. A method according to any one of the preceding claims, wherein the one or more separate sections are selected from pumps, inserts, mixing units, wet mills, stirred tanks, and homogenizers.   6. A method according to any one of the preceding claims, wherein one or more separate sections are coupled to the stirring vessel via a pump circulation system.   The method according to any one of claims 1 to 6, characterized in that the average solid substance content of the suspension is in the range of 70 to 1000 g / l.   8. A transition metal according to any one of claims 1 to 7, characterized in that the transition metal is selected from Ni, Mn, Co and optionally one or more further metals selected from alkali metals, aluminum and magnesium. the method of.   The method according to any one of claims 1 to 8, wherein the precipitated transition metal hydroxide is separated from the mother liquor, and particles having a particle size of more than 50 µm are separated.   10. The method according to claim 9, wherein particles of transition metal hydroxide having a particle size exceeding 30 [mu] m are separated.